EP0757070B1 - Verfahren zur Herstellung eines Gegenstandes durch Spritzgiessen eines Stärkeproduktes - Google Patents

Verfahren zur Herstellung eines Gegenstandes durch Spritzgiessen eines Stärkeproduktes Download PDF

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Publication number
EP0757070B1
EP0757070B1 EP96202192A EP96202192A EP0757070B1 EP 0757070 B1 EP0757070 B1 EP 0757070B1 EP 96202192 A EP96202192 A EP 96202192A EP 96202192 A EP96202192 A EP 96202192A EP 0757070 B1 EP0757070 B1 EP 0757070B1
Authority
EP
European Patent Office
Prior art keywords
starch
water
article
weight
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96202192A
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English (en)
French (fr)
Other versions
EP0757070A3 (de
EP0757070A2 (de
Inventor
Kornelis Fester Gotlieb
Dick De Wit
Diane Trudy Pluimers
Herman Feil
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cooperative Avebe UA
Original Assignee
COOEPERATIEVE VERKOOP- EN PRODUCTIEVERENIGING VAN AARDAPPELMEEL EN DERIVATEN 'AVEBE' BA
Cooperative Avebe UA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from NL1000936A external-priority patent/NL1000936C2/nl
Application filed by COOEPERATIEVE VERKOOP- EN PRODUCTIEVERENIGING VAN AARDAPPELMEEL EN DERIVATEN 'AVEBE' BA, Cooperative Avebe UA filed Critical COOEPERATIEVE VERKOOP- EN PRODUCTIEVERENIGING VAN AARDAPPELMEEL EN DERIVATEN 'AVEBE' BA
Publication of EP0757070A2 publication Critical patent/EP0757070A2/de
Publication of EP0757070A3 publication Critical patent/EP0757070A3/de
Application granted granted Critical
Publication of EP0757070B1 publication Critical patent/EP0757070B1/de
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products

Definitions

  • the invention relates to the manufacture of articles by injection moulding starch products.
  • the injection moulding of starch is known from EP-B-0 118 240 and EP-B-0 304 401.
  • EP-B-0 118 240 starch is plasticized in the presence of water and optionally of additives at an elevated temperature and pressure to obtain a homogeneous melt. This melt is injected into a mould and the thus-moulded article, upon cooling to below its glass rubber transition temperature, is taken from the mould and is then ready for use.
  • EP-B-0 304 401 discloses a technique to be carried out in two steps, whereby first granules are formed by forcing starch, in the presence of water and optional additives, through an extruder, whereafter the extruded material is cooled and granulated.
  • the granules obtained can be stored, transported, etc. and can thereafter be processed, often by a different company, into the desired articles according to the known injection moulding technique.
  • the principal object of the invention is to provide a method for improving the water resistance of articles manufactured by injection moulding starch products.
  • articles manufactured by injection moulding a starch product are obtained which are better resistant to the action of water vapour, for instance to air humidity.
  • such article is treated, according to the invention, with an aqueous solution of an ammonium and/or magnesium sulphate or with a mixture of water and a water-miscible organic solvent.
  • This treatment entails virtually no flocculation at the surface of the article.
  • the water resistance is considerably improved.
  • the effects caused by the action of the water are twofold: on the one hand, the water provides a suitable medium for allowing relaxation of the stresses in the starch molecules in that the frozen condition is terminated, and on the other hand the aqueous environment enables the starch molecules to recrystallize to a greater or lesser extent. Both effects contribute to the envisaged improvement of the water resistance.
  • the presence of ammonium sulphate, magnesium sulphate or a water-miscible organic solvent causes the article to absorb only little water during the treatment, so that flocculation at the surface of the articles is largely or practically completely avoided.
  • compositions which mainly contain starch and in addition, in most cases, further contain urea and, in a number of cases, a copolymer of ethylene and acrylic acid (see “Tabelle 2" on p. 54). From those compositions, samples are manufactured by injection moulding, which samples are immersed in water to investigate their water resistance ("4.3 Wasserresistenz" on pp. 57-58).
  • eligible for use as starch is any starch, modified or not, that is plastically deformable at elevated temperature.
  • native starch such as potato starch
  • chemically and/or enzymically converted or partially decomposed starch types such as crosslinked starch, crosslinked or non-crosslinked starch ethers or starch esters, starch types partially decomposed chemically and/or enzymically, etc.
  • the starch can be of any origin, for instance from potatoes, wheat, maize, waxy maize, etc.
  • the term starch as used herein encompasses both native starch and modified starch types.
  • Starches by nature contain a certain amount of water and that water is of importance because it contributes as a natural plasticizer to the plastic deformability of the starch.
  • one or more supplementary plasticizers are used, such as glycerol, sorbitol, propylene glycol, (peta)erytritol or polyalkylene oxides with a low molecular weight. The added amount thereof is usually between 5 and 50% by weight, calculated on the starch product.
  • thermoplastic condition it is advantageous to add so-called flow improvers, which are also referred to as lubricants and which effect a better processability in the thermoplastic condition.
  • flow improvers which are also referred to as lubricants and which effect a better processability in the thermoplastic condition.
  • suitable flow improvers are animal and vegetable oils and fats, preferably in hydrogenated form, and fatty acids as well as fatty acid derivatives such as mono and diglycerides or phosphatides. Castor oil and lecithin are examples of particularly suitable flow improvers or lubricants.
  • the amount of flow improver in the starch product or the starch composition is usually at most 10% by weight.
  • the starch is partly formed by a starch hydrolysate.
  • Starch hydrolysates are starches which have been obtained by partially decomposing native or modified starch through chemical or enzymic hydrolysis for the purpose of obtaining a starch with a shorter chain and a correspondingly lower molecular weight.
  • DE dextrose equivalent
  • a starch hydrolysate with a DE ⁇ 40 and more preferably with a DE in the range of 5 to 30 is used.
  • Such starch hydrolysates are commercially available.
  • the use of starch hydrolysates as described above has a favourable effect on the starch composition to be thermoplastically deformed in the sense that the mobility or liquidity of this last is improved, so that the stresses resulting from the injection moulding process can more readily be carried off.
  • the water resistance of the injection moulded article can sometimes even be improved considerably, so that the use of starch hydrolysates further enhances the effect of the invention.
  • the total starch comprises at most 40% by weight, and more preferably 10 to 30% by weight, of a starch hydrolysate with a DE ⁇ 40.
  • starch hydrolysate like the use of the above-discussed lubricants such as castor oil and lecithin, has the additional effect that often a smaller amount of plasticizer such as glycerol can be used. Accordingly, by the use of starch hydrolysate a more flexible total system is obtained, since it provides more possibilities of varying the components and the mutual ratio thereof, as a function of the eventual injection moulded product it is desired to manufacture.
  • water-soluble salts in the starch product.
  • Those salts can contribute to the prevention of flocculation at the surface of the injection moulded article when it is being treated in accordance with the invention, but their most important effect is to render the injection moulded articles better resistant to the action of water vapour, which is present, for instance, in the ambient air. So, the moisture resistance is improved.
  • This effect is clearly distinct from the better water resistance obtainable through the present treatment and can also be achieved, through the measure mentioned, i.e. through the inclusion of water-soluble salts in the starch product, in an injection moulded product which has not been subjected to the present treatment.
  • Water-soluble salts that can be included in the starch product are preferably inorganic salts, in particular ammonium sulphate and/or magnesium sulphate.
  • the amount of salt is fairly large and is generally 5 to 30% by weight, calculated on the starch product.
  • fillers such as lime, chalk, silicon oxide, magnesium oxide, etc.
  • organic fillers and specifically organic biodegradable reinforcing natural fibrous materials such as cellulose fibers, cotton, etc.
  • Fillers have a material-saving and a reinforcing effect and natural fiber materials have a further advantage in that they do not leave any harmful residues when after use the injection moulded article is discarded as waste.
  • fillers and in particular reinforcing fibrous material are used in an amount of at most 50% by weight.
  • the injection moulded article can be manufactured in one as well as in two steps.
  • starch chosen and additives if any, for instance as specified above, are mixed with each other in the desired mutual ratios to form a relatively homogeneous starch composition.
  • starch product as used herein is meant the starch composition that is intended to be processed into an article through injection moulding, that is, including additives such as plasticizers, flow improvers, salts, fillers, etc.
  • the ratios of the various components should obviously be chosen so that in effect a mixture is obtained that is thermoplastically deformable under the temperature and pressure conditions used in the injection moulding. Further, due account should also be taken of the desired fluidity, strength, water resistance, moisture resistance, etc.
  • Mixing can be performed in any suitable mixing device and the mixture obtained is then, in the first case, supplied directly to an injection moulding machine, where the mixture first turns into a melt, which is injected into a mould, whereafter the article is taken from the mould after it has cooled to below its glass rubber transition temperature.
  • the mixture is pressed through an extruder and the extruded material is cooled and granulated.
  • the granules can then be used as a feed for feeding the injection moulding machine, optionally much later and at another company.
  • the mixing of the components can also take place directly in the injection moulding machine or in the extruder.
  • the article After the article has been manufactured by injection moulding as described above, it possesses, as stated, a water resistance that is insufficient for numerous applications.
  • the water resistance is considerably improved by treating the article for some time with an aqueous solution of ammonium sulphate and/or magnesium sulphate or with a mixture of water and a water-miscible organic solvent.
  • an aqueous solution of ammonium sulphate and/or magnesium sulphate or with a mixture of water and a water-miscible organic solvent.
  • mixtures of water and water-miscible organic solvents such as lower alcohols, in particular ethanol.
  • the mixing ratio can easily be determined by the skilled person. In the case of ethanol, the volume ratio of water to ethanol is preferably in the range of 10/90 to 90/10 and most preferably in the range of 40/60 to 70/30.
  • the treatment of the article obtained by injection moulding with water in which a specific inorganic salt or a water-miscible solvent is included, as described earlier, can be carried out in various ways.
  • the article is immersed in the aqueous treatment liquid, so that a uniform wetting is obtained.
  • the article can be moved in the treatment liquid and/or this last can be stirred.
  • the temperature at which the treatment is carried out is not particularly critical. Usually, work proceeds at room temperature, but a slightly lower temperature also gives good results, while a slightly increased temperature of, for instance, 30-50°C accelerates the process in the sense that the better water resistance envisaged is achieved faster.
  • the duration of the treatment can vary strongly, depending inter alia on the means used to prevent flocculation, the conditions under which the treament is carried out and the desired extent of improvement of the water resistance. In general, however, the duration of the treatment is between 1 and 90 minutes.
  • the article After the article has been treated in the manner described hereinabove, it can optionally be wiped dry or it can simply be allowed to dry and thus the treatment can be concluded. It has been found, however, that a short concluding treatment with water for, for instance, 1 to 60 seconds, for instance by rinsing the article with water, can yield a further improvement of the intended better water resistance, especially when the treatment time with the aqueous treatment liquid according to the invention is chosen to be fairly short, for instance shorter than about 15 minutes. While the first treatment apparently causes the relief of stresses present in the injection moulded article, the second treatment, i.e. just rinsing with water for a short time, enables a certain extent of recrystallization to occur. Both effects appear to contribute to the improved water resistance contemplated according to the invention.
  • the improved water resistance of articles obtained according to the invention can be determined with various tests.
  • the water absorption can be determined after the articles have been immersed in water for certain periods of time. Further, it can be determined when the article breaks when it is subjected to load in water.
  • the treatment with an aqueous treatment liquid according to the invention is carried out in such a manner that the water absorption by the treated article, when it is immersed in water for one hour at room temperature, is at most 50% by weight and most preferably at most 30% by weight.
  • the articles obtained according to the invention because of their high water resistance, are better resistant to warp or loss of their original shape than are articles which have not been afterwards treated by the present method. They are therefore better suited as packaging material or for any other application where the articles come or may come into contact with water and it is of importance that they then retain their original shape as well as possible.
  • packaging material that can come into contact with an aqueous environment for a limited time, etc.
  • the articles can easily be biologically decomposed without leaving harmful residues. So they are environment-friendly.
  • the extruded material is injection moulded in an injection moulding machine Demag D60 NCIII-K, which is equipped with a standard screw.
  • the mould temperature is 20°C and the temperature profile over the barrel is as follows: -------------------------170/180/180/180°C.
  • test rods are injection moulded according to DIN 23167.
  • test 1 For determining water absorption, a test rod is immersed in water for a particular time (60 minutes) and then dried and weighed. From the weight increase the water absorption in percent by weight is calculated (test 1).
  • tests 2 and 8 further tests are carried out, in which in a number of cases additionally 20 parts by weight of magnesium sulphate are added to the extruder (tests 2 and 8) and in a number of cases the test rods obtained are first treated (immersed) in an aqueous liquid of the composition specified below, for the period of time specified below (tests 3-8) before the water absorption is determined.
  • tests 3-8 the test rods obtained are first treated (immersed) in an aqueous liquid of the composition specified below, for the period of time specified below (tests 3-8) before the water absorption is determined.
  • test 1 7 test rods are made. Six test rods are then treated with a saturated aqueous solution of ammonium sulphate and of magnesium sulphate, respectively, for 1 minute, 5 minutes and 60 minutes.
  • test rods thus treated and the untreated test rod are then subjected to a test for determining their resistance in contact with water under a constant load.
  • the test rods are vertically suspended in a water bath of 20°C, half immersed therein. Clamped to the lower end of the rods is a weight of 2 kg. Then the yield time is determined, i.e. the point in time when the test rods breaks in two.
  • test 1 9 test rods are made.
  • One test rod is not treated, two test rods are treated with a mixture of ethanol and water for 5 minutes and 6 test rods are treated with a saturated aqueous solution of ammonium sulphate and of magnesium sulphate, respectively, for 1 minute, 5 minutes and 60 minutes.
  • test rods are immersed for 5 minutes in an aqueous ink solution and the thickness of the ink layer or the depth of ink penetration is determined.
  • test rods are made.
  • a number of test rods are treated with a saturated aqueous solution of magnesium sulphate for different periods of time, and this treatment may or may not be followed by a treatment with water for 1 second.
  • Other test rods are treated with a saturated aqueous solution of ammonium sulphate, likewise for different periods of time and likewise followed or not followed by a treatment with water for 1 second.
  • Yet other test rods are treated for 5 minutes with different mixtures of ethanol and water.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Biological Depolymerization Polymers (AREA)

Claims (12)

  1. Verfahren zur Herstellung eines Artikels durch Spritzgießen eines Stärkeprodukts, wonach die Wasserfestigkeit des erhaltenen Artikels verbessert wird, indem dieser mit einer wäßrigen Lösung von Ammoniumsulfat und/oder Magnesiumsulfat oder mit einer Mischung aus Wasser und einem mit Wasser mischbaren organischen Lösemittel behandelt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Artikel mit einer gesättigten Lösung aus Ammoniumsulfat und/oder Magnesiumsulfat behandelt wird.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Artikel mit einer Mischung aus Wasser und Ethanol in einem Volumenverhältnis von 10/90 - 90/10 behandelt wird.
  4. Verfahren nach den Ansprüchen 1-3, dadurch gekennzeichnet, daß die Behandlungsdauer des Artikels zwischen 1 und 90 Minuten liegt.
  5. Verfahren nach den Ansprüchen 1-4, dadurch gekennzeichnet, daß bei der beschriebenen Behandlung eine Nachbehandlung mit Wasser für 1 bis 60 Sekunden erfolgt.
  6. Verfahren nach den Ansprüchen 1-5, dadurch gekennzeichnet, daß in dem Stärkeprodukt ein Salz enthalten ist.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß Ammoniumsulfat und/oder Magnesiumsulfat in dem Stärkeprodukt in einem Menge von 5 bis 30 Gewichtsprozent enthalten ist.
  8. Verfahren nach den Ansprüchen 1-7, dadurch gekennzeichnet, daß zusätzlicher Weichmacher in dem Stärkeprodukt in einer Menge von 5 bis 50 Gewichtsprozent vorhanden ist.
  9. Verfahren nach den Ansprüchen 1-8, dadurch gekennzeichnet, daß ferner ein Fließverbesserungsmittel wie Biberöl oder Lecithin im Stärkeprodukt in einer Menge von höchstens 10 Gewichtsprozent enthalten ist.
  10. Verfahren nach den Ansprüchen 1-9, dadurch gekennzeichnet, daß das Stärkeprodukt höchstens 40 Gewichtsprozent und vorzugsweise 10-30 Gewichtsprozent eines Stärkehydrolysats mit einem DE <40, vorzugsweise mit einem DE im Bereich von 5 bis 30, aufweist.
  11. Verfahren nach den Ansprüchen 1-10, dadurch gekennzeichnet, daß ferner ein verstärkendes Naturfasematerial im Stärkeprodukt in einer Menge von höchstens 50 Gewichtsprozent enthalten ist.
  12. Verfahren nach den Ansprüchen 1-11, dadurch gekennzeichnet, daß das Stärkeprodukt vollständig oder größtenteils aus nativer Kartoffelstärke besteht oder, im Falle eines Stärkehydrolysats, daraus abgeleitet ist.
EP96202192A 1995-08-04 1996-08-05 Verfahren zur Herstellung eines Gegenstandes durch Spritzgiessen eines Stärkeproduktes Expired - Lifetime EP0757070B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
NL1000936A NL1000936C2 (nl) 1995-08-04 1995-08-04 Werkwijze voor het vervaardigen van een voorwerp door spuitgieten van een zetmeelprodukt.
NL1000936 1995-08-04
NL1001036 1995-08-23
NL1001036A NL1001036C1 (nl) 1995-08-04 1995-08-23 Werkwijze voor het vervaardigen van een voorwerp door spuitgieten van een zetmeelprodukt.

Publications (3)

Publication Number Publication Date
EP0757070A2 EP0757070A2 (de) 1997-02-05
EP0757070A3 EP0757070A3 (de) 1997-10-01
EP0757070B1 true EP0757070B1 (de) 2003-01-29

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96202192A Expired - Lifetime EP0757070B1 (de) 1995-08-04 1996-08-05 Verfahren zur Herstellung eines Gegenstandes durch Spritzgiessen eines Stärkeproduktes

Country Status (5)

Country Link
EP (1) EP0757070B1 (de)
AT (1) ATE231894T1 (de)
DE (1) DE69625966T2 (de)
DK (1) DK0757070T3 (de)
NL (1) NL1001036C1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10062848C1 (de) * 2000-12-11 2002-04-04 Biop Biopolymer Gmbh Wasserformbeständiges, thermoplastisches Stärkematerial, Verfahren zu dessen Herstellung und dessen Verwendung
NL1029163C2 (nl) * 2005-06-01 2006-12-04 Paperfoam B V Inrichting en houder voor het verpakken van een informatiedrager.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BG46154A3 (en) * 1983-02-18 1989-10-16 Warner Lambert Co Method for preparing of capsules
GB2208651B (en) * 1987-08-18 1991-05-08 Warner Lambert Co Shaped articles made from pre-processed starch
US4839450A (en) * 1987-11-17 1989-06-13 The United States Of America As Represented By The Secretary Of Agriculture Moisture-shrinkable films from starch graft copolymers
US5576049A (en) * 1992-12-04 1996-11-19 Franz Haas Waffelmaschinen Industriegesellschaft M.B.H. Process of manufacturing rottable thin-walled starch-based shaped elements

Also Published As

Publication number Publication date
DE69625966T2 (de) 2003-11-27
DE69625966D1 (de) 2003-03-06
NL1001036C1 (nl) 1997-02-07
ATE231894T1 (de) 2003-02-15
EP0757070A3 (de) 1997-10-01
DK0757070T3 (da) 2003-05-19
EP0757070A2 (de) 1997-02-05

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